18 research outputs found
Investigation of the Jahn-Teller Transition in TiF3 using Density Functional Theory
We use first principles density functional theory to calculate electronic and
magnetic properties of TiF3 using the full potential linearized augmented plane
wave method. The LDA approximation predicts a fully saturated ferromagnetic
metal and finds degenerate energy minima for high and low symmetry structures.
The experimentally observed Jahn-Teller phase transition at Tc=370K can not be
driven by the electron-phonon interaction alone, which is usually described
accurately by LDA.
Electron correlations beyond LDA are essential to lift the degeneracy of the
singly occupied Ti t2g orbital. Although the on-site Coulomb correlations are
important, the direction of the t2g-level splitting is determined by the
dipole-dipole interactions. The LDA+U functional predicts an aniferromagnetic
insulator with an orbitally ordered ground state. The input parameters U=8.1 eV
and J=0.9 eV for the Ti 3d orbital were found by varying the total charge on
the TiF ion using the molecular NRLMOL code. We estimate the
Heisenberg exchange constant for spin-1/2 on a cubic lattice to be
approximately 24 K. The symmetry lowering energy in LDA+U is about 900 K per
TiF3 formula unit.Comment: 7 pages, 9 figures, to appear in Phys. Rev.
Atomic structure of sodium iron phosphate glasses
The atomic structure of a series of sodium iron phosphate glasses is studied using different experimental techniques: X-ray and neutron diffraction (ND), infrared spectroscopy, extended X-ray absorption fine structure (EXAFS), and X-ray absorption near-edge structure (XANES). Detailed information about the atomic pair correlations is obtained. The high resolution of ND in real space resolves two P–O distances at 1.48 Ǻ and 1.59 Ǻ as expected. All the glasses are found to consist of a phosphate tetrahedral network with metaphosphate chains and pyrophosphate units, and every phosphate unit is found to have two or three nonbridging oxygen (NBO) links available to coordinate with Na and Fe cations. The Fe–O coordination number in these glasses is found to decrease from 5.7 to 4.8 with increasing the Fe content, whereas the Na coordination number of approximately 5 is detected for all the samples